Structure‐Activity Relationships of Glucose‐based PdII‐Bis(NHC) Complexes in a Model Suzuki‐Miyaura Reaction

Abstract

The authors of this work have optimized a novel synthetic route towards glucose‐based PdII‐bis(NHC) complexes in only 4 steps with total yields up to 73 %. The synthesis route encompasses an Appel reaction towards 6‐iodo‐glucopyranosides, followed by acyl‐protection, then quaternization with imidazoles and finally the conversion of these acyl‐protected glucosyl imidazolium salts to their respective palladium(II)bis(NHC) complexes, via an intermediary silver(I) complex. Overall, 11 acyl‐protected glucosyl imidazolium iodides as NHC‐precursors and 15 complexes have been synthesized. The structure‐activity relationships of different functionalizations in these complexes and their reactivity in a model Suzuki‐Miyaura between bromobenzene and 4‐tolueneboronic acid reaction has been investigated, and a highly reactive complex leading to >99 % yield at 0.005 mol% catalytic loading has been found.